ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 10, pp. 1686−1691. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © L.L. Semenycheva, E.V. Geras’kina, Yu.O. Matkivskaya, A.A. Moikin, Yu.A. Kurskii,
2015, published in Zhurnal Prikladnoi Khimii, 2015,
Vol. 88, No. 10, pp. 1505−1510.
AND POLYMERIC MATERIALS
Structure of the Copolymers of Alkyl Methacrylate and Vinyl
Alkyl Ethers, Novel Viscosity Modiﬁ ers of Lubricating Oils
L. L. Semenycheva
, E. V. Geras’kina
, Yu. O. Matkivskaya
A. A. Moikin
, Yu. A. Kurskii
Lobachevsky State University of Nizhny Novgorod, pr. Gagarina 23, Nizhny Novgorod, 603950 Russia
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
ul. Tropinina 49, Nizhny Novgorod, 603137 Russia
Received February 6, 2015
Abstract—Copolymers of vinyl butyl ethers and alkyl methacrylates may ﬁ nd use as resource-saving viscosity
modiﬁ ers of oils that is due to a new approach to their synthesis, which allows reaching high compositional ho-
mogeneity of the polymer chain. The data of
C NMR spectroscopy were reported which show the structure of
alternating copolymers obtained by compensation copolymerization in boiling monomer under the radical initiation.
Polymers based on vinyl monomers are traditionally
used as thickening additives for lubricating oils. Such
polymers as polyalkyl methacrylates, polymers of
vinyl-n-butyl ether (VBE), which are of good thickening
efﬁ ciency but low resistance to thermal and mechanical
degradation, are well-known [1–4]. Recently, special
attention is paid to this characteristic of lubricating oils
since it is associated with the problem of the life of oil
and, consequently, resource saving and the environment.
Previously, copolymers of alkyl methacrylates and vinyl
butyl esters obtained in compensation polymerizations in
the boiling monomers at radical initiation were proposed
as viscosity modiﬁ ers [5–8]. They are highly resistant
to mechanical degradation in solutions of mineral and
synthetic oils [5–7]. This behavior is due to composition
and structure of the copolymers: the ester unit/ether unit
ratio of the copolymer according to IR and
spectroscopy is close to 50 : 50, and since relative
activity of ether in these pairs is close to zero; this fact is
an indirect evidence of alternating copolymer structure.
In this paper using copolymers of methyl methacrylate
(MMA) and butyl acrylate (BA) with vinyl alkyl ether,
obtained by compensation polymerization in
monomer under a radical initiation, an investigation
was conducted by
C NMR spectroscopy.
We used commercial vinyl isobutyl ether (ViBE)
(Sigma-Aldrich CAS N 109-53-5), VBE (Sigma-
Aldrich CAS N 111-34-2), BA (Sigma-Aldrich CAS
N 141-32-2), MMA (Sigma-Aldrich CAS N 80-62-6),
azobisisobutyronitrile AIBN (Sigma-Aldrich CAS
N 78-67-1). The synthesis of copolymers was carried
out according to a previously proposed method : to a
boiling vinyl alkyl ether (VAE) ester solution containing
0.15 mol % AIBN (based on the active monomer) was
dosed with a constant volumetric ﬂ ow. Total comonomer
ratio was 1 : 4. After completing the dosing the mixture
was heated at reﬂ ux temperature of VAE another 20 min
and then it was cooled; unreacted VAE was distilled.
Synthesis of polyvinyl ether (PVBE) was performed by
dosing the monomer to its boiling portion. The volume
of the dosed monomer was 90% of the total.
The resulting copolymer samples were dried to
constant weight at a pressure of 10
MPa; structure and